91949-05-2Relevant academic research and scientific papers
o-Isocyanobenzyl complexes of transition metals as novel organometallic isocyanide ligands, (η5-C5H5)M(CO)3(o-CH 2C6H4NC) (M = Mo, W) and Mn(CO)5(o-CH2C6H4NC). Synthesis and reactivity toward palladium(II) and platinum(II) substrates
Facchin, Giacomo,Uguagliati, Paolo,Michelin, Rino A.
, p. 1818 - 1822 (2008/10/08)
Organometallic isocyanides of the general formula o-([M]CH2)C6H4NC ([M] = CpMo(CO)3, CpW(CO)3 (Cp = η5-C5H5), Mn(CO)5) were prepared by reaction of o-(ICH2)C6H4NC with the corresponding metal carbonyl anion. They are slightly foul-smelling solids that are stable for months under an inert atmosphere in the cold and in the dark. All the analytical and spectroscopic data confirm the uncoordination of the isocyanide function. Its coordinating capability has been tested in reactions involving Pd(II) and Pt(II) substrates and leading to the formation of heterobinuclear complexes of the type cis-M′Cl2(PR3)-(CN CH2[M]) (M′ = Pd, Pt; PR3 = PPh3; [M] = CpMo(CO)3, CpW(CO)3, Mn(CO)5; M′ = Pt; PR3 = PMePh2, [M] = CpW(CO)3) and heterotrinuclear species of the type cis-M′Cl2(CN CH2[M])2 (M′ = Pd, Pt; [M] = CpW(CO)3). Insertion reaction of [W]CH2 NC into the Pt-H bond of trans-PtHCl(PPh3)2 gives the formimidoyl derivative trans-PtCl(PPh3)2(CHN CH2[W]). Although the isocyanide groups in the [M]CH2 NC complexes are sterically incapable of chelation, they can potentially undergo insertion into the adjacent M-C σ-bond or intermolecular carbonyl substitution. However the thermal behavior of the [Mo]CH2 NC and [W]CH2 NC ligands shows extensive decomposition without any evidence for the occurrence of such reactions. Heating of [Mn]CH2 NC leads instead to the dimer [Mn(CO)4(o-CH2C6H4NC)]2 in which the isocyanobenzyl moiety bridges two Mn(CO)4 groups and whose structure was assigned by analogy of its IR spectrum with that of the o-cyanobenzyl analogue [Mn(CO)4(o-CH2C6H4CN)]2.
